Oxidative Dyeing Compositions Comprising an 1-Hexyl/Heptyl-4,5-diaminopyrazole and a m-Aminophenol and Derivatives Thereof

ABSTRACT

Compositions for the oxidative dyeing of keratin fibers, in particular human keratin fibers, comprising (A) a 1-hexyl/heptyl-4,5-diaminopyrazole compound of the general formula (I), its physiologically compatible water-soluble salt, or mixtures thereof and; (B) a m-aminophenol compound of the general formula (II), its physiologically compatible water-soluble salt, or mixtures thereof; and (C) an oxidizing agent. 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8  and R 9  are as defined herein and a=1 or 2.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application claims the benefit of U.S. Provisional Application No.61/445,265, filed on Feb. 22, 2011.

FIELD OF THE INVENTION

The present invention relates to a composition for the oxidative dyeingof keratin fibers, in particular human keratin fibers, comprising (A) a1-hexyl/heptyl-4,5-diaminopyrazole compound as defined in formula (I)hereafter, its physiologically compatible water-soluble salt or mixturesthereof and, (B) a m-aminophenol compound of the general formula (II) asdefined hereafter, its physiologically compatible water-soluble salt, ormixtures thereof, and (C) an oxidizing agent.

BACKGROUND OF THE INVENTION

The oxidative dyeing of hair is one of the most extensively used methodsto color hair. In this process oxidative hair coloring precursors areused in combination with an oxidizing agent, commonly a peroxy oxidizingagent. The precursors are generally small molecules capable of diffusinginto hair, generally comprising primary intermediates and couplers. Awide variety of primary intermediates and couplers have been employed insuch oxidative hair coloring compositions. Selections of specificcombinations of couplers and primary intermediates allow reaching thedesired nuance of hair color.

Besides providing the desired color, the dye precursors used foroxidative hair dyeing have to also meet some additional requirements.Indeed, the combination of couplers and primary intermediates usedshould deliver the desired intensity together with good wash andbleeding fastness and be acceptable from a toxicological anddermatological point of view.

Pyrazole compounds have been disclosed as oxidative dye precursors. Acolorant for keratin fibers, which is not mixed with an oxidant beforeuse, is free from manganese salts and consists of a combination suitablefor coloring keratin fibers in the presence of atmospheric oxygen in asuitable cosmetic medium is known. The combination comprises: (a)4,5-diaminopyrazole compound(s); and (b) compound(s) selected from5-amino-2-methylphenol(s) and/or m-phenylenediamine compound(s) or theirphysiologically-compatible salts. See for example EP 1,166,748A2.

Oxidation colorant compositions containing a combination of at least one4,5-diaminopyrazole compound as a primary intermediate and at least onehalogenated m-aminophenol as a secondary intermediate are known. See forexample US 2003/0000027.

A composition for the oxidative dyeing of hair based on a combination ofprimary intermediate substances and coupler substances contains, asprimary intermediate substance, a diaminopyrazole compound, including4,5-diamino-1-(2-hydroxyethyl) pyrazole is known. See for example U.S.Pat. No.5,061,289.

Furthermore, these disclosures do not disclose an example with aselection of a C6/C7 straight chain alkyl substituent on the N-1position of a 4,5-diaminopyrazole.

The compositions, known in the prior art, comprising pyrazole compoundsare usually not satisfactory, especially in terms of intensity, washfastness and bleeding.

Thus, there is a need to develop new compositions for the oxidativedyeing of hair providing satisfactory color intensity along with goodwash fastness and bleeding properties.

The invention provides novel dye compositions that overcome knowndrawbacks of pyrazole compounds. In particular the invention providesgood hair color intensity together with good wash and bleeding fastness.Indeed, it has surprisingly been found that the modification of thepyrazole ring system on the N-1 position by a C6/C7 straight alkyl chaincombined with aminophenol couplers provides excellent properties ofresistance to the various treatments which keratinous fibers mayundergo.

SUMMARY OF THE INVENTION

The present invention relates to a composition for the oxidative dyeingof keratin fibers, in particular human keratin fibers, comprising (A) a1-hexyl/heptyl-4,5-diaminopyrazole compound of the general formula (I),its physiologically compatible water-soluble salt, or mixtures thereofand; (B) a m-aminophenol compound of the general formula (II), itsphysiologically compatible water-soluble salt, or mixtures thereof; and(C) an oxidizing agent.

wherein R₁, R₂, R₃, R⁴, R⁵, R₆, R₇, R₈ and R₉ are as defined in theclaims and a=1 or 2.

The present invention also relates to a method of dyeing hair comprisingthe steps of applying this composition to hair, and to a kit comprising:(i) a tint component comprising at least (a) a1-hexyl/heptyl-4,5-diaminopyrazole compound of the general formula (I)or a physiologically compatible water-soluble salt, or mixtures thereofand; (b) a m-aminophenol compound of the general formula (II), itsphysiologically compatible water-soluble salt, or mixtures thereof, and(ii) a developer component comprising (c) an oxidizing agent.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, the term “composition for the oxidative dyeing ofkeratin fibers” means a ready-to-use composition in a suitable carriermedium for dyeing keratin fibers, in particular human hair, comprisingoxidative dye precursors (primary intermediates and couplers) and anoxidizing agent. These compositions can typically be the result of amixture of two compositions namely a tint component comprising the dyeprecursors and usually an alkalizing agent such as ammonia and/ormonoethanolamine and a developer component comprising the oxidizingagent.

As used herein, the term “keratin” refers to a scleroprotein found inepidermal tissues and modified into hard structures such as horns, hair,and nails. As used herein, the term “hair” refers to keratinous fiberson a living, e.g. a person, or non-living body, e.g. in a wig,hairpiece, or other aggregation of non-living keratinous fibers.Mammalian, preferably human, hair is preferred. Notably, hair, wool,fur, and other keratinous fibers are suitable substrates for coloring bythe compounds and compositions described herein.

As used herein, the term “dye precursors” refers to compounds that maybe used in the composition to act as primary intermediates, couplers, orboth, in order to provide color to ketatinous fibers.

It is to be understood that when this development refers to a particularstructure, all of the reasonable additional tautomeric structures areincluded. In the art, tautomeric structures are frequently representedby one single structure and the invention follows this general practice.

Pyrazole Compound

The 1-hexyl/heptyl-4,5-diaminopyrazole compound of the invention is ofthe general formula (I), its physiologically compatible water-solublesalt or mixtures thereof:

wherein a is equal to one or two;

wherein R₁ is selected from the group consisting of:

(a) C-linked substituents selected from the group consisting of:

-   -   (i) substituted or unsubstituted, straight or branched or        cyclic, saturated or unsaturated, aliphatic or heteroaliphatic        substituents, in particular alkyl or hydroxy substituted alkyl,    -   (ii) substituted or unsubstituted, mono- or poly-unsaturated        aromatic or heteroaromatic substituents, in particular aryl or        heteroaryl,

wherein said C-linked substituents comprise from 1 to 6 carbon atoms andfrom 0 to 5 heteroatoms selected from the group consisting of O, F, N, Pand Si;

(b) S-linked substituents selected from the group consisting of SA¹,SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²;

(c) O-linked substituents selected from the group consisting of OA¹,ONA¹A²;

(d) N-linked substituents selected from the group consisting of NA¹A²;(NA¹A²A³)⁺, NA¹SA², NO₂; NA¹A²;

(e) halogens selected from the group consisting of F, Cl, Br, and I; and

(f) hydrogen;

wherein A¹, A², and A³ are independently selected from the groupconsisting of hydrogen; substituted or unsubstituted, straight orbranched or cyclic, saturated or unsaturated, aliphatic orheteroaliphatic or aromatic or heteroaromatic substituents, preferablysubstituted or unsubstituted alkyl, or A¹ and A² together with nitrogenatoms to which they are bound form a ring; wherein said substituents orring comprise from 1 to 6 carbon atoms and from 0 to 5 heteroatomsselected from the group consisting of O, S, N, P, and Si;

R₂ and R₃ are selected independently of each other from the groupconsisting of a hydrogen atom; a C1-C6 alkyl substituent; atrifluoromethyl substituent; a C1-C6 aminoalkyl substituent; a C1-C6hydroxyalkyl substituent; C1-C6 an alkoxyalkyl substituent.

Suitable salts of formula (I) are for example chlorides, bromides,sulfates, malates, tartrates, lactates and acetates. Of particularinterest is the hemisulfate salt, which can provide a better stabilityduring storage than other salts such as chloride or sulfate.

In a preferred embodiment the 1-hexyl/heptyl-4,5-diaminopyrazolecompound (I) is a compound with formula (I.1):

wherein a is equal to one or two.

The 1-hexyl/heptyl-4,5-diaminopyrazole compounds of formula (I) arecombined with a m-aminophenol compound of formula (II) in order toprovide a resulting hair color with excellent washfastness, bleedingfastness, and intensity.

m-aminophenol Compound

The m-aminophenol compound of the invention is according to the generalformula (II) below, or a physiologically compatible water-soluble saltthereof:

wherein R₄, R₅, R₆, R₇ are substituents selected independently of eachother from the group consisting of:

(a) C-linked substituents selected from the group consisting of:

-   -   (i) substituted or unsubstituted, straight or branched or        cyclic, saturated or unsaturated, aliphatic or heteroaliphatic        substituents, in particular alkyl or hydroxy substituted alkyl    -   (ii) substituted or unsubstituted, mono- or poly-unsaturated        aromatic or heteroaromatic substituents, in particular aryl or        heteroaryl,

wherein said C-linked substituents comprise from 1 to 10 carbon atomsand from 0 to 5 heteroatoms selected from the group consisting of O, F,N, P and Si;

(b) S-linked substituents selected from the group consisting of SA¹,SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²;

(c) O-linked substituents selected from the group consisting of OA¹,ONA¹A²;

(d) N-linked substituents selected from the group consisting of NA¹A²;(NA¹A²A³)⁺, NA¹SA², NO₂; NA¹A²;

(e) halogens selected from the group consisting of F, Cl, Br, and I; and

(f) hydrogen;

wherein A¹, A², and A³ are independently selected from the groupconsisting of: hydrogen; substituted or unsubstituted, straight orbranched or cyclic, saturated or unsaturated, aliphatic orheteroaliphatic or aromatic or heteroaromatic substituents, preferablysubstituted or unsubstituted alkyl, or A¹ and A² together with nitrogenatoms to which they are bound form a ring; wherein said substituents orring comprise from 1 to 10 carbon atoms and from 0 to 5 heteroatomsselected from the group consisting of O, S, N, P, and Si;

wherein R₈ and R₉ are substituents selected independently of each otherfrom the group consisting of:

(g) C-linked substituents selected from the group consisting of:

-   -   (i) substituted or unsubstituted, straight or branched or        cyclic, saturated or unsaturated, aliphatic or heteroaliphatic        substituents, in particular alkyl or hydroxy substituted alkyl    -   (ii) substituted or unsubstituted, mono- or poly-unsaturated        aromatic or heteroaromatic substituents, in particular aryl or        heteroaryl,

wherein said C-linked substituents comprise from 1 to 6 carbon atoms andfrom 0 to 5 heteroatoms selected from the group consisting of O, F, N, Pand Si;

(h) hydrogen.

Suitable salts of formula (II) are for example chlorides, bromides,sulfates, malates, tartrates, lactates and acetates.

In preferred embodiments, R₅ and R₆ are hydrogen, R₄ and R₇ areindependently selected from hydrogen, halogens, C1-C6 alkyl and C2-C6hydroxalkyl, C2-C4 alkoxy and mixtures thereof and R₈ and R₉ areindependently selected from hydrogen, C1-C3 alkyl or C1-C3 hydroxyalkyl,C1-C4 alkoxyalkyl and mixtures thereof.

In a preferred embodiment the m-aminophenol compound (II) is a compoundwith formula (II.1):

In another preferred embodiment the m-aminophenol compound (II) is acompound with formula (II.2):

In another preferred embodiment the m-aminophenol compound (II) is acompound with formula (II.3):

In another preferred embodiment the m-aminophenol compound (II) is acompound with formula (II.4):

In another preferred embodiment the m-aminophenol compound (II) is acompound with formula (II.5):

In another preferred embodiment the m-aminophenol compound (II) is acompound with formula (II.6):

In another preferred embodiment the m-aminophenol compound (II) is acompound with formula (II.7):

In another preferred embodiment the m-aminophenol compound (II) is acompound with formula (II.8):

The m-aminophenol compound (II) may of course be a mixture of differentm-aminophenol compounds falling under the definition of (II), inparticular a mixture of any of the compounds II.1 to 11.8.

It has surprisingly been found that the modification of the pyrazolering system in N-1-position by a C6/C7 straight alkyl chain provides adye precursor which couples with a m-aminophenol compound to giveexcellent properties of resistance to the various treatments whichkeratinous fibers may undergo, in particular washfastness and resistanceto bleeding.

Oxidizing Agent

The compositions of the invention comprise an oxidizing agent. Typicalsuitable oxidizing agents for the oxidative dyeing of keratin fibers maybe selected from hydrogen peroxide, sodium periodate, urea peroxide,melamine peroxide, perborates, percarbonates, perphosphates,persilicates, persulfates, oxidizing enzymes such as uricases, oxidases,and peroxidases, and mixtures thereof. Hydrogen peroxide, perborates, orpercarbonates may be preferred.

Another potential oxidizing agent for use herein is a source ofperoxymonocarbonate ions. Preferably, such a source is formed in situfrom a source of hydrogen peroxide and a hydrogen carbonate ion source.Such an oxidizing agent has been found to be particularly effective at apH of up to and including 9.5, preferably from about 7.5 to about 9.5more preferably about pH 9. Moreover, this system is also particularlyeffective in combination with a source of ammonia or ammonium ions.

Accordingly, any source of these peroxymonocarbonate ions may beutilized. Suitable sources for use herein include sodium, potassium,guanidine, arginine, lithium, calcium, magnesium, barium or ammoniumsalts of carbonate, carbamate and hydrocarbonate ions and mixturesthereof. In particular, sodium carbonate, sodium hydrogen carbonate,potassium carbonate, potassium hydrogen carbonate, guanidine carbonate,guanidine hydrogen carbonate, lithium carbonate, calcium carbonate,magnesium carbonate, barium carbonate, ammonium carbonate, ammoniumhydrogen carbonate and mixtures thereof may be preferred. Percarbonatesalts may also be utilized to provide both the source of carbonate ionsand as an oxidizing agent. Preferred sources of carbonate ions,carbamate and hydrocarbonate ions are sodium hydrogen carbonate,potassium hydrogen carbonate, ammonium carbonate, ammonium carbamate,and mixtures thereof.

The hair dyeing composition may usually comprise from about 1% to about15% by total weight of the composition, typically from about 1.5% toabout 10% by weight, and more typically from about 2% to about 8% byweight of the oxidizing agent relative to the total weight of thecomposition.

The oxidizing agent may be provided in a developer component which ismixed to a tint component to obtain the composition of the invention.The developer component may be based on any desired formulation chassis,including any commercial product, for example an oil-in-water emulsion.Typical developer components comprise about 6% or about 9% of H₂O₂ bytotal weight of the composition. A commercial example is the Welloxon®Emulsion with respectively about 6% and about 9% H₂O₂, marketed by Wellaand comprising as INCI ingredients: Water, Hydrogen Peroxide, CetearylAlcohol, Ceteareth-25, Salicylic Acid, Phosphoric Acid, DisodiumPhosphate, Etidronic Acid.

The hair dyeing composition of the invention may be formed as thickliquid, cream, gel, emulsion, foam, aerosol mousse or as a solid form towhich water is added to generate the oxidant and form a thickenedvehicle suitable for hair coloring. They may comprise in addition to theingredients indicated above further ingredients in order to furtherenhance the properties of the composition, including but not limited to:solvents; oxidative dyes, direct dyes; oxidizing agents; radicalscavengers; thickeners and or rheology modifiers; chelants; pH modifiersand buffering agents; carbonate ion sources; peroxymonocarbonate ionsources; anionic, cationic, nonionic, amphoteric or zwitterionicsurfactants, or mixtures thereof; anionic, cationic, nonionic,amphoteric or zwitterionic polymers, or mixtures thereof; fragrances;enzymes; dispersing agents; peroxide stabilizing agents; antioxidants;natural ingredients, e.g. proteins and protein compounds, and plantextracts; conditioning agents including silicones and cationic polymers,ceramides, preserving agents; and opacifiers and pearling agents (suchas titanium dioxide and mica). Some adjuvants referred to above, but notspecifically described below, which are suitable are listed in theInternational Cosmetics Ingredient Dictionary and Handbook, (8th ed.;The Cosmetics, Toiletry, and Fragrance Association). Particularly, vol.2, sections 3 (Chemical Classes) and 4 (Functions) are useful inidentifying specific adjuvants to achieve a particular purpose ormultipurpose. A few of these ingredients are discussed hereinbelow,whose disclosure is of course non-exhaustive.

Alkalizing Agent

The composition for the oxidative dyeing of keratin fibers may furthercomprise, generally in the tint component, an alkalizing agent as knownin the art. Any alkalizing agent known in the art may be used such asammonia, alkanolamines for example monoethanolamine, diethanolamine,triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3-propanediol, guanidium salts, alkali metaland ammonium hydroxides such as sodium hydroxide, alkali metal andammonium carbonates, and mixtures thereof. Typical alkalizing agents areammonia and/or monoethanolamine.

Typically, the compositions for the oxidative dyeing of keratin fiberscomprise from about 0.1% to about 10%, preferably from about 0.5% toabout 6%, more preferably from about 1% to about 4% by weight of thealkalizing agent relative to the total weight of the composition.

Primary Intermediates

In addition to the pyrazole compounds of the invention, the hair dyeingcompositions of the invention may comprise further primaryintermediates. Suitable primary intermediates for use in thecompositions described herein include, but are not limited to:toluene-2,5-diamine, p-phenylenediamine, N-phenyl-p-phenylenediamine,N,N-bis(2-hydroxyethyl)-p-phenylenediamine,2-hydroxyethyl-p-phenylenediamine,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine),2-methoxymethyl-p-phenylenediamine,2-(1,2-dihydroxyethyl)-p-phenylenediamine,2,2′-(2-(4-aminophenylamino)ethylazanediyl)diethanol,2-(2,5-diamino-4-methoxyphenyl)propane-1,3-diol,2-(7-amino-2H-benzo[b][1,4]oxazin-4(3H)-yl)ethanol,2-chloro-p-phenylenediamine, p-aminophenol, p-(methylamino)phenol,4-amino-m-cresol, 2-methoxy-p-phenylenediamine,2,2′-methylenebis-4-aminophenol, 2,4,5,6-tetraminopyrimidine,2,5,6-triamino-4-pyrimidinol, 1-hydroxyethyl-4,5-diaminopyrazolesulfate, 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-ethylpyrazole,4,5-diamino-1-isopropylpyrazole, 4,5-diamino-1-butylpyrazole,4,5-diamino-1-pentylpyrazole, 4,5-diamino-1-benzylpyrazole,2,3-diamino-6,7-dihydropyrazolo[1,2-a]pyrazol-1(5H)-onedimethosulfonate, salts thereof (for example chlorides, bromides,sulfates, malates, tartrates, lactates and acetates) and mixturesthereof.

Of particular interest are toluene-2,5-diamine, p-phenylenediamine,2-hydroxyethyl-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine,2-(2,5-diamino-4-methoxyphenyl)propane-1,3-diol,2-chloro-p-phenylenediamine, 2-methoxy-p-phenylenediamine,2-((2-(4-amino-phenylamino)-ethyl)-(2-hydroxyethyl)-amino)-ethanol,their salts and combinations.

Typically, the compositions for the oxidative dyeing of keratin fiberscomprise from about 0.1% to about 10%, preferably from about 0.3% toabout 6%, more preferably from about 0.5% to about 4% by weight of theprimary intermediates relative to the total weight of the composition.

Couplers

In addition to the m-aminophenol compounds of the invention, the hairdyeing compositions of the invention may comprise other couplers toobtain various shades. Suitable couplers for use in the compositionsdescribed herein include, but are not limited to: resorcinol,4-chlororesorcinol, 2-chlororesorcinol, 2-methylresorcinol,4,6-dichlorobenzene-1,3-diol, 2,4-dimethylbenzene-1,3-diol,m-aminophenol, 4-amino-2-hydroxytoluene,2-methyl-5-hydroxyethylaminophenol, 3-amino-2,6-dimethylphenol,3-amino-2,4-dichlorophenol, 5-amino-6-chloro-o-cresol,5-amino-4-chloro-o-cresol, 6-hydroxybenzomorpholine,2-amino-5-ethylphenol, 2-amino-5-phenylphenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 2-amino-5-ethoxyphenol,5-methyl-2-(methylamino)phenol, 2,4-diaminophenoxyethanol,2-amino-4-hydroxyethylamino anisole,1,3-bis-(2,4-diaminophenoxy)-propane,2,2′-(2-methyl-1,3-phenylene)bis(azanediyl)diethanol,benzene-1,3-diamine, 2,2′-(4,6-diamino-1,3-phenylene)bis(oxy)diethanol,3-(pyrrolidin-1-yl)aniline, 1-(3-(dimethylamino)phenyl)urea,1-(3-aminophenyl)urea, 1-naphthol, 2-methyl-1-naphthol,1,5-naphthalenediol, 2,7-naphthalenediol or1-acetoxy-2-methylnaphthalene, 4-chloro-2-methylnaphthalen-1-ol,4-methoxy-2-methylnaphthalen-1-ol, 2,6-dihydroxy-3,4-dimethylpyridine,2,6-dimethoxy-3,5-pyridinediamine,3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine,2,6-diaminopyridine, pyridine-2,6-diol, 5,6-dihydroxyindole,6-hydroxyindole, 5,6-dihydroxyindoline,3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, 1,2,4-trihydroxybenzene,2-(benzo[d][1,3]dioxo1-5-ylamino)ethanol (also known ashydroxyethyl-3,4-methylenedioxyaniline), and mixtures thereof.

When the composition is obtained by mixing a tint component and adeveloper component, additional primary intermediates and couplers maybe preferably incorporated in the tint component.

Typically, the compositions for the oxidative dyeing of keratin fiberscomprise from about 0.1% to about 10%, preferably from about 0.3% toabout 6%, more preferably from about 0.5% to about 4% by weight of thecouplers relative to the total weight of the composition.

Direct Dyes

The compositions of the present invention may also comprise compatibledirect dyes, in an amount sufficient to provide additional coloring,particularly with regard to intensity. Typically, such an amount willrange from about 0.05% to about 4%, by weight of the direct dyesrelative to the total weight of the composition. When the composition isobtained by mixing a tint component and a developer component, thedirect dyes are usually incorporated in the tint component.

The following direct dyes are commonly used: Acid dyes such as AcidYellow 1, Acid Orange 3, Acid Black 1, Acid Black 52, Acid Orange 7,Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Violet 43, HC Blue 16,Acid Blue 62, Acid Blue 25, Acid Red 4, Basic Dyes such as Basic Brown17, Basic Red 118, Basic Orange 69, Basic Red 76, Basic Brown 16, BasicYellow 57, Basic Violet 14, Basic Blue 7, Basic Blue 26, Basic Red 2,Basic Blue 99, Basic Yellow 29, Basic Red 51, Basic Orange 31, BasicYellow 87,4-(3-(4-amino-9,10-dioxo-9,10-dihydroanthracen-l-ylamino)propyl)-4-methylmorpholin-4-ium-methylsulfate,(E)-1-(2-(4-(4,5-dimethylthiazol-2-yl)diazenyl)phenyl)(ethyl)amino)ethyl)-3-methyl-1H-imidazol-3-iumchloride,(E)-4-(2-(4-(dimethylamino)phenyl)diazenyl)-1-methyl-1H-imidazol-3-ium-3-yebutane-1-sulfonate,(E)-4-(4-(2-methyl-2-phenylhydrazono)methyl)pyridinium-1-yl)butane-1-sulfonate,N,N-dimethyl-3-(4-(methylamino)-9,10-dioxo-4a,9,9a,10-tetrahydroanthracen-1-ylamino)-N-propylpropan-1-aminiumbromide, Disperse Dyes such as Disperse Red 17, Disperse Violet 1,Disperse Red 15, Disperse Violet 1, Disperse Black 9, Disperse Blue 3,Disperse Blue 23, Disperse Blue 377, Nitro Dyes such as1-(2-(4-nitrophenylamino)ethyl)urea,2-(4-methyl-2-nitrophenylamino)ethanol, 4-nitrobenzene-1,2-diamine,2-nitrobenzene-1,4-diamine, Picramic acid, HC Red No. 13,2,2′-(2-nitro-1,4-phenylene)bis(azanediyl)diethanol, HC Yellow No. 5, HCRed No. 7, HC Blue No.2, HC Yellow No. 4, HC Yellow No. 2, HC Orange No.1, HC Red No. 1, 2-(4-amino-2-chloro-5-nitrophenylamino)ethanol, HC RedNo. 3, 4-amino-3-nitrophenol, 4-(2-hydroxyethylamino)-3-nitrophenol,2-amino-3-nitrophenol, 2-(3-(methylamino)-4-nitrophenoxy)ethanol,3-(3-amino-4-nitrophenyl)propane-1,2-diol, HC Yellow No. 11, HC VioletNo. 1, HC Orange No. 2, HC Orange No. 3, HC Yellow No. 9, HC Red No. 10,HC Red No. 11, 2-(2-hydroxyethylamino)-4,6-dinitrophenol, HC Blue No.12, HC Yellow No. 6, HC Yellow No. 12, HC Blue No. 10, HC Yellow No. 7,HC Yellow No. 10, HC Blue No. 9, 2-chloro-6-(ethylamino)-4-nitrophenol,6-nitropyridine-2,5-diamine, HC Violet No. 2,2-amino-6-chloro-4-nitrophenol, 4-(3-hydroxypropylamino)-3-nitrophenol,HC Yellow No. 13, 6-nitro-1,2,3,4-tetrahydroquinoxaline, HC Red No. 14,HC Yellow No. 15, HC Yellow No. 14,N2-methyl-6-nitropyridine-2,5-diamine,N1-allyl-2-nitrobenzene-1,4-diamine, HC Red No. 8, HC Green No.1, HCBlue No. 14, and Natural dyes such as Annato, Anthocyanin, Beetroot,Carotene, Capsanthin, Lycopene, Chlorophyll, Henna, Indigo, Cochineal.

Thickeners

The hair dyeing compositions of the present invention may comprise athickener in an amount sufficient to provide the composition with aviscosity so that it can be readily applied to the hair without undulydripping off the hair and causing mess. Typically, such an amount willbe at least 0.05%, preferably at least 0.5%, more preferably at least1%, by weight of thickener relative to the total weight of thecomposition. When the composition is obtained by mixing severalcomponents, the thickener may be present in any of the components.

Preferred for use herein are salt tolerant thickeners, including but notlimited to: xanthan, guar, hydroxypropyl guar, scleroglucan, methylcellulose, ethyl cellulose (available as AQUACOTE™), hydroxyethylcellulose (NATROSOL™), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (available as KLUCEL™), hydroxyethyl ethylcellulose, cetyl hydroxyethyl cellulose (available as NATROSOL™) Plus330), N-vinylpyrollidone (available as POVIDONE™), Acrylates/Ceteth-20Itaconate Copolymer (available as STRUCTURE™ 3001), hydroxypropyl starchphosphate (available as STRUCTURE™ ZEA), polyethoxylated urethanes orpolycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDI copolymer(available as ACULYN™ 44), PEG-150/Stearyl/SMDI copolymer available asACULYN™ 46), Acrylates/Beheneth-25 Methacrylate Copolymer (available asACULYN™ 28), Acrylates/Vinyl Neodecanoate Crosspolymer (available asACULYN™ 38), Acrylates/Steareth-20 Methacrylate Crosspolymer (availableas ACULYN™ 88), PEG-150 Distearate (available as ACULYN™ 60),trihydroxystearin (available as THIXCIN™), acrylates copolymer (e.g.available as ACULYN™ 33) or hydrophobically modified acrylate copolymers(e.g. Acrylates/Steareth-20 Methacrylate Copolymer (available as ACULYN™22), non-ionic amphophilic polymers comprising at least one fatty chainand at least one hydrophilic unit selected from polyether urethanescomprising at least one fatty chain.

Also preferred for use herein are thickeners based on lamellar gelnetwork systems, comprising at least one surfactant or amphophile havingan HLB of 6 or less and a melting point of at least 30° C., preferablyselected from fatty alcohols comprising from 14 to 30 carbon atoms, oroxyethylenated fatty alcohols comprising from 16 to 30 carbon atoms and2 units or less of ethylene oxide, and further comprising at least oneionic or nonionic surfactant, preferably selected from:

-   -   anionic surfactants selected from C8-C30 alkyl sulfates,        preferably C12-C18 alkyl sulfates,    -   anionic surfactants according to the formula R_(n)X_(m)YM,        wherein R is independently selected from alkyl, alkenyl or        alkylaryl groups having from 8 to 30 carbon atoms, X is        independently selected from polar groups comprising at least one        carbon atom and at least one oxygen or nitrogen atom, Y is an        anionic group selected from carboxylates, sulfates, sulfonates        or phosphates, n and m are independently 1 or 2, and M is        hydrogen or a salt forming cation and mixture thereof, most        preferably selected from C8-C30 alkyl ether phosphates having        from 1 to 20, preferable 2 to 10 ethylene oxide units (e.g.        available as CRODAFOS™ CES);    -   non-ionic surfactant comprising one or more polyethyleneoxide        chains, preferably each polyethyleneoxide chain has on average        at least 50 ethylene oxide units and most preferably 100 to 200        ethylene oxide units (e.g. available as VOLPO™ S200),    -   cationic surfactants selected from quaternary ammonium salts or        amido-amines having at least one fatty chain, preferably        comprising at least 16 carbon atoms and most preferably at least        20 carbon atoms,    -   and mixture thereof.

Examples of such lamellar gel network systems are disclosed inEP1,832,273 and EP2,103,299.

The composition preferably comprises a mixture of cetearyl alcohol anddicetyl phosphate and ceteth-10 phosphate (e.g. available as CRODAFOS™CES).

Chelants

The compositions of the present invention may comprise chelants in anamount sufficient to reduce the amount of metals available to interactwith formulation components, particularly oxidizing agents, moreparticularly peroxides and percarbonates. Typically, such an amountrange from at least 0.15%, preferably at least 0.25%, by weight of thechelants relative to the total weight of the composition. Suitablechelants for use herein include but are not limited to:diethylenetriamine-N,N′,N″-polyacids, diethylenetriaminepentaacetic acid(DTPA), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP),diamine-N,N′-dipolyacid, monoamine monoamide-N,N′-dipolyacid, andN,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid chelants(preferably EDDS (ethylenediaminedisuccinic acid)), carboxylic acids(preferably aminocarboxylic acids), phosphonic acids (preferablyaminophosphonic acids) and polyphosphoric acids (in particular straightpolyphosphoric acids), their salts and derivatives. When the compositionis obtained by mixing a tint component and a developer component, thechelants may be incorporated in the tint component or in the developercomponent or in both. A chelant is usually present in developercomponents for stability reason.

pH Modifiers

The compositions of the present invention may comprise in addition tothe alkalizing agent discussed above a pH modifier and/or bufferingagent in an amount that is sufficiently effective to adjust the pH ofthe composition to fall within a range from about 3 to about 13,preferably from about 8 to about 12, more preferably from about 9 toabout 11.

Radical Scavengers

According to the present invention, the compositions may comprise aradical scavenger. As used herein the term radical scavenger refers to aspecies that can react with a radical, to convert the radical species bya series of fast reactions to an unreactive or less reactive species.The radical scavenger is also preferably selected such that it is not anidentical species as the alkalising agent and is present in an amountsufficient to reduce the damage to the hair during thecoloring/bleaching process. The compositions of the present inventioncomprise a radical scavenger from about 0.1% to about 10%, preferablyfrom about 1% to about 7% by weight of the radical scavenger relative tothe total weight of the composition.

Suitable radical scavengers for use herein may be selected from theclasses of alkanolamines, amino sugars, amino acids, esters of aminoacids and mixtures thereof. Suitable compounds include3-substituted-pyrazol-5-ones, 3-carboxy-1H-pyrazol-5-one,3-methyl-1-phenyl-pyrazol-5-one, 3-methyl-1-p-tolyl-pyrazol-5-one,3-methyl-1-(4-sulfophenyl)-pyrazol-5-one,3-methyl-1-(4-sulfoamidophenyl)-pyrazol-5-one,3-methyl-1-(3-sulfophenyl)-pyrazol-5-one,3-methyl-1-(3-sulfoamidophenyl)-pyrazol-5-one,3-methyl-1-(2-chloro-5-sulfophenyl)-pyrazol-5-one,3-methyl-1-(2,5-dichloro-4-sulfophenyl)-pyrazol-5-one,3-methyl-1-(4-chlorophenyl)-pyrazol-5-one,3-methyl-1-(4-carboxyphenyl)-pyrazol-5-one,3-carboxy-1-phenyl-pyrazol-5-one,3-carboxy-1-(4-sulfophenyl)-pyrazol-5-one, 1,3-diphenyl-pyrazol-5-one,methyl pyrazol-5-one-3-carboxylate, 3-amino-1-propanol,4-amino-1-butano1,5-amino-1-pentanol, 1-amino-2-propanol,1-amino-2-butanol, 1-amino-2-pentanol, 1-amino-3-pentanol,1-amino-4-pentanol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine,N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine,histidine, sarcosine, serine, glutamic acid, tryptophan, or mixturesthereof, or the salts, such as the potassium, sodium, or ammonium saltsthereof, or mixtures thereof. In some embodiments, the inventivecompositions may comprise glycine, sarcosine, lysine, serine,2-methoxyethylamine, glucosamine, glutamic acid, morpholine, piperidine,ethylamine, 3-amino-l-propanol, or mixtures thereof.

Method of Hair Dyeing

In order to use the dyeing composition, the tint component and developercomponents are usually mixed immediately prior to use and a sufficientamount of the mixture is applied to the hair, according to the hairabundance, generally from about 60 to about 250 grams. Upon suchpreparation the composition is applied to the hair to be dyed andremains in contact with the hair for an amount of time effective to dyethe hair. Typically, the hair dye composition is allowed to act on thehair from about 2 to about 60, preferably about 15 to about 45, morepreferably about 30 minutes, at a temperature ranging from 15° C. toabout 50° C. Thereafter, the hair is rinsed with water to remove thecomposition and dried. If necessary, the hair is washed with a shampooand rinsed, e.g., with water or a weakly acidic solution, such as acitric acid or tartaric acid solution, and dried. Optionally, a separateconditioning product may also be provided.

The method of dyeing hair with the composition may therefore comprisethe steps of:

(i) providing a tint component comprising (a) a1-hexyl/heptyl-4,5-diaminopyrazole compound of the general formula (I)as defined in claim 1 its physiologically compatible water-soluble salt,or mixtures thereof and, (b) a m-aminophenol compound of the generalformula (II) as defined in claim 1, its physiologically compatiblewater-soluble salt, or mixtures thereof;

(ii) providing a developer component comprising (c) an oxidizing agent;

(iii) mixing the tint component and the developer component to obtain acomposition for the oxidative dyeing of keratin fibers according to thecomposition of the invention;

(iv) applying said composition for the oxidative dyeing of keratinfibers onto the hair.

The method may further comprise waiting a period of time, typicallybetween 2 minutes and 60 minutes, and then rinsing the composition fromthe hair.

The compositions can be applied on hair via applicator bottle or brush.It can be used on full head or partly on single strands (highlightapplication) as common highlight applicator foils, caps and specialapplicators can be used, but also freehand techniques such as balayage,with brush and/or combs can be possible. The composition can also beapplied as a mousse via a manual spray, a pressurized container or anaerosol mousse.

The composition may be dispensed as a solid form to which water is addedto generate the oxidant and form a thickened vehicle suitable for haircoloring.

The dye combination of the invention may also be used in threecomponents system. See for example disclosed US2010/0223739A2 assignedto L'Oreal. Such a process and kit for lightening or dyeing keratinfibers may comprise the following composition applied to the hairfibers: an aqueous cosmetic composition (A) comprising at least onefatty substance and at least one surfactant; a cosmetic composition (B)comprising at least one alkaline agent and the oxidative dyes of theinvention and if present direct dyes and other oxidative dyes, acosmetic composition (C) comprising at least one oxidizing agent,wherein the amount of the at least one fatty substance in composition(A) is greater than 20% by weight relative to the total weight ofcomposition (A).

Methods of Making—Kit

The composition, and its tint component and developer component, may bemanufactured by conventional processes known in the art formanufacturing oxidative dyeing products, and ad-mixing the ingredientsof each component composition in suitable vessels, followed by packagingin appropriate individual containers. The components may be for examplepackaged in plastic or aluminium bottles.

In particular, the present invention may be provided as a kit comprisingdifferent components to be mixed by the consumer or salon stylist toobtain a hair dyeing composition according to the invention. Such a kitmay comprise:

(i) a tint component comprising (a) a 1-hexyl/heptyl-4,5-diaminopyrazolecompound of the general formula (I) as defined above, itsphysiologically compatible water-soluble salt, or mixtures thereof and,(b) a m-aminophenol compound of the general formula (II) as definedabove, its physiologically compatible water-soluble salt, or mixturesthereof, and

ii) a developer component comprising an oxidizing agent.

The kit may be presented in a single package comprising separatecontainers for the tint component, the developer component, andoptionally a conditioner, a color refresher or other hair treatmentproduct, instructions for use, gloves. The instructions for use includethe steps of the method described above and optionally provide visualcues or pictures for the desired steps of the method. Kits are usuallysold in retail products with enough material in each component forpreparing a hair dyeing composition for one use.

The composition may be dispensed as a foam using for examplemanually-actuable, non-aerosol dispenser such as a pump or squeezefoamers, aerosol mousse. See for example EP 613,728 B1, WO 97/013585 A1,EP 1,716,933A1, U.S. Pat. No. 3,709,437, U.S. Pat. No. 3,937,364, U.S.Pat. No. 4,022,351, U.S. Pat. No. 4,147,306, U.S. Pat. No. 4,184,615,U.S. Pat. No. 4,615,467 and FR 2,604,622. One particular example of asqueeze foamer useful herein is able to dispense from an upright orinverted position such as the one discussed in U.S. Pat. No. 6,604,693assigned to Taplast, and more specifically, at column 2, line 65,through column 4, line 67 of that patent.

The composition may be dispensed as a solid form to which water is addedto generate the oxidant and form a thickened vehicle suitable for haircoloring.

EXAMPLES

The following are non-limiting examples of the compositions of thepresent invention. The examples are given solely for the purpose ofillustration and are not to be construed as limitations of the presentinvention, as many variations thereof are possible without departingfrom the spirit and scope of the invention, which would be recognized byone of ordinary skill in the art. All concentrations are listed asweight percent, unless otherwise specified.

The compositions tested were formulated by mixing a tint componentaccording to the formulation below with a developer component in a 1:1ratio. The developer component is a commercially available Welloxondeveloper at 6% (20 vol) peroxide concentration. In all the tests, whitehair was used (1.5 g/tress). 3 g tint component+3 g developer componentwere applied for each tress for 30 minutes at 30° C. The tresses wererinsed for 2 minutes including 30 second shampooing.

TABLE 1 Tint Component Formulations Ingredients Weight % Lanolin alcohol2.0 Glyceryl Stearate 5.5 Glycol Distearate 2.0 Cetearyl alcohol and SLS17.5 (90:10 mix) Sodium cocoyl isethionate 0.46 Sodium laureth sulfate4.0 Ascorbic acid 0.3 Sodium sulfate 0.179* Sodium sulfite 0.4 DisodiumEDTA 0.1 Alkyl Pyrazole salts X Coupler Y Ammonia, 28.3% in water 6.40Fragrance 0.25 Reverse osmosis water QS to 100% Total Wt *C5 and C8formulations at 0.001% and NaCl added at 0.292% to take into account thedifferent salts used as source of the pyrazoles.

X and Y were calculated in function of the molecular weight of the alkylpyrazole and the coupler to reach a final molar concentration of ca.0.025 M for each compound in the tint component formulation.

TABLE 2 Tint component formulations with a further primary intermediate(2,5-toluenediamine sulfate) Ingredients Weight % Lanolin alcohol 2.0Glyceryl Stearate 5.5 Glycol Distearate 2.0 Cetearyl alcohol and SLS(9:1) 17.5 Sodium cocoyl isethionate 0.46 Sodium laureth sulfate 4.0Ascorbic acid 0.3 Sodium sulfate 0.179* Sodium sulfite 0.4 Disodium EDTA0.1 Sodium chloride 0.292 C5 pyrazole salt 0.434 Or Or C6 pyrazole salt0.463 Or Or C8 Pyrazole salt 0.521 3-amino-2,6-dimethylphenol 0.3432,5-toluenediamine sulfate (DTS) 0.110 Ammonia, 28.3% in water 6.43Fragrance 0.25 QS to 100% with reverse osmosis QS to 100% water Total Wt*C5 and C8 formulations at 0.001%

The quantity of pyrazole varies to achieve the same molar concentrationof about 0.025M in combination with DTS.

Color Intensity

The tint component indicated above was formulated withalkyldiaminopyrazoles having varying alkyl chain length and differentaminophenol compounds. After mixing with the developer component, theresulting mixture was applied to white hair and rinsed. The resultingcolor was measured using a colorimeter and characterized by the L*value. An L* of 100 is considered white and L* of 0 is considered black,therefore the higher the L* value the lower the color intensity. Themeasured L* values for the different primary dye combinations of Table 1are summarized in Table 3 below.

TABLE 3 Comparison of L* values for the tints of Table 1

  (II.1)

  (II.2)

  (II.3)

  (II.4) C3  

27.05 38.25 37.17 36.95 C5  

26.17 38.7  35.6  37.38 C6  

26.49 37.77 36.57 38.95 C7  

29.03 40.06 38.78 41.6  C8  

34.42 43.97 43.27 44.58The measured L* values for the different primary dye combinations ofTable 2 are summarized in Table 4 below.

TABLE 4 Comparison of L* values for the tints of Table 2

C5  

33.37 C6  

32.73 C8  

34.61

Tables 3 and 4 demonstrate that the L* values of hair tresses dyed withthe C8 alkyldiaminopyrazole combined with the selected couplers aresignificantly higher compared to the other alkyldiaminopyrazoles withthe same selected couplers, correlating with weaker color. As the C8alkyldiaminopyrazole with the selected couplers clearly does not givethe desired color intensity, it will not be further analyzed or comparedto the present invention.

Diffusion Testing

The diffusion testing protocol measures the ability for the dye to staywithin the hair when the fibers are wet. In this test, dyed tresses ofhair were prepared as indicated above and then separately immersed in a1 litre beaker containing 900.0 g water. The beaker was placed in thecenter of a stir plate and the tress attached to a clamping device thatwas used to lower the tress into the beaker. When in the beaker, thetress remained above the stir bar in the center of the beaker. The tresswas lowered until the water line was at the top of the hair tress. Thestir plate was turned on so that the stir bar would spin atapproximately 100 rpm. All tresses were tested at the same spin rate.The tress was left in the beaker with stir bar rotating for three hours.After the three hours, the tresses were removed. The absorbance spectrumof the remaining solution was measured using a UV-vis spectrophotometerto characterize the amount of dye that diffused out of the hair into thesolution. A full absorbance spectrum from 400 to 700 nm was measured andthe absorbance at the peak maximum was measured for each case.

The absorbance values measured were normalized taking C6 Pyrazole asreference and are summarized in Table 5 below.

TABLE 5 Comparison of Color in Solution Diffusion Testing Relative to C6Pyrazole (normalized to 1.0)

  (II.2)

  (II.3)

  (II.4) C3  

2.16 2.12 1.69 C5  

1.45 1.20 1.27 C6  

1.00 1.00 1.00 C7  

0.65 0.66 0.84

This test shows that the C6 and C7 alkyldiaminopyrazoles areconsistently leaching less dye materials into solution than the C3alkyldiaminopyrazole and C5 alkyldiaminopyrazole, having, in most cases,a better than two-fold improvement compared to the C3alkyldiaminopyrazole. This implies that less color diffuses from thehair tresses containing the C6 and C7 relative to the C3 and C5alkyldiaminopyrazoles.

Wash Fade Test

The wash fade measures the fading of the color after repeated washcycles (up to 24). In this test, five hair tresses are dyed and theinitial color measurements are obtained, one is retained for reference.Shampoo is then applied according to this procedure. The four remaininghair tresses are thoroughly wetted for 30 sec. 0.1 g of a conventionalshampoo per gram of hair (e.g.: 0.1 g shampoo for each 1.0 g tress) isapplied. The shampoo is applied with a syringe using a zigzag actiondown the length of the hair. The shampoo is milked into hair for 30secs, ensuring even application, at a speed of less than 30 strokes/60seconds (for example-1 stroke every 2 seconds) using a ‘2 fingers andthumb’ action.

The shampoo is then rinsed according to this procedure: the rinse watertemperature is set to 37° C.±1° C. and flow-rate to 4±0.5 1/min. Thesprayer is held at an angle to the tresses and the tresses are rinsedfor 30 seconds while gently stroking the shampoo out of the hair (20strokes total). Multiple tresses may be rinsed at the same time, as longas water is running over all tresses. A total time of 30 seconds and atotal of 20 strokes should be used for multiple tresses. After rinsing,starting at the top of the tress, the tress is squeezed between fingersto remove excess water (one stroke).

The tresses are then dried according to the procedure: the tresses arelaid onto a clean paper towel and blotted gently. The tresses are held10 cm from a blow dryer (set to high heat) and dryed 1.5 min while usingfingers to separate the hair. If needed, the hair is brushed gentlytwice. The tresses are turned over and dried 1.5 min while using fingersto separate the hair. If needed, hair is brushed gently twice. Betweenwashings, hair tresses are kept out of light; either wrapped in aluminumfoil or stored in a drawer.

This procedure is repeated on the remaining four hair tresses for eachdye sample. Color readings are taken at the 3^(rd), 6^(th), 9^(th),12^(th), 15^(th), 18^(th), 21^(st) and 24^(th) shampoo/rinse/dry cyclewashing intervals. At the 6^(th), 12^(th), 18^(th) and 24^(th)shampoo/rinse/dry cycle one hair tress is retained for colormeasurements and visual assessments.

For the present experiment, C3, C5, C6 and C7 alkyldiaminopyrazoles weretested in combination with an aminophenol of formula (II.3), accordingto formulations of Table 1:

The starting value (0 wash cycle) of for each combination of dyes wastaken as a reference and the delta ΔE*=√((ΔL*)²+(Δa*)²+(Δb*)²) valueswere calculated for each cycle relative to it:ΔE_(x)*=√((L_(x)*−L₀*)²+(a_(x)*−a₀*)²+(b_(x)*−b₀*)²). The results aresummarized in the Table 6 below:

TABLE 6 Wash fade testing result of hair dyed withN¹-alkyldiaminopyrazoles and compound II.3 showing differences relativeto initial (t₀) readings. Cycle C7 C6 C5 C3 0 0 0 0 0 3 0.81 0.54 2.833.10 6 1.61 1.62 3.48 2.77 9 1.28 1.69 3.82 5.74 12 1.33 1.77 3.77 6.1815 1.93 1.91 3.56 7.13 18 2.16 2.18 4.36 7.62 21 1.84 2.48 4.97 7.14 242.02 2.80 4.78 6.81

As can be seen on Table 6, this experiment demonstrates a higher rate ofloss of color from hair tresses dyed in the following order C3>C5>C6>C7.

Towel Bleeding

A consumer relevant measure of the ability to see differences inwashfastness is to assess how much color from wet dyed hair tressestransfers to a white cloth, such as a white wash cloth. The amounts oftowel bleeding resulting from washed tresses dyed with a C5alkyldiaminopyrazole and C6 alkyldiaminopyrazole with compound offormula (II.3) were measured using conventional ΔE* measurements.

The testing method is summarized below:

After washing a dyed hair switch, place switch on a white cloth (50%cotton, 50% polyester) with an average color reading of L*=95.8,a*=−1.40 and b*=0.897 Fold cloth in half over the hair switches. Place a2.27 kg weight on folded cloth for 5 min. Upon removal of the hair,visual inspection shows a larger and more intense stain for the C5alkyldiaminopyrazole compared to the C6 alkyldiaminopyrazole compound.The noticeability of the stain on the cloth is calculated using the ΔE*measurements for C5 and C6 relative to the cloth (see ΔE* values below).

TABLE 7 Total change in cloth color (ΔE*) due to dye transfer from wettresses dyed with C5 and C6 alkyldiaminopyrazoles. C5 C6

  (II.3) ΔE = 4.5112 ΔE = 1.9258

  (II.3) + DTS ΔE = 2.09  ΔE = 1.58 

It was found that the C6 alkyldiaminopyrazole dye had a stain intensitywhich is less noticeable than the C5 alkyldiaminopyrazole dye after onewash cycle.

Concluding Remark

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross-referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A composition for the oxidative dyeing of keratin fibers, inparticular human keratin fibers, comprising: (A) a1-hexyl/heptyl-4,5-diaminopyrazole compound of the general formula (I),a physiologically compatible water-soluble salt thereof, or mixturesthereof,

wherein a is equal to one or two; wherein R₁ is selected from the groupconsisting of: (a) C-linked substituents selected from the groupconsisting of: (i) substituted or unsubstituted, straight or branched orcyclic, saturated or unsaturated, aliphatic or heteroaliphaticsubstituents, in particular alkyl or hydroxy-substituted alkyl, and (ii)substituted or unsubstituted, mono- or poly-unsaturated aromatic orheteroaromatic substituents, in particular aryl or heteroaryl, whereinsaid C-linked substituents comprise from 1 to 6 carbon atoms and from 0to 5 heteroatoms selected from the group consisting of O, F, N, P andSi; (b) S-linked substituents selected from the group consisting of SA¹,SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²; (c) O-linkedsubstituents selected from the group consisting of OA¹ and ONA¹A²; (d)N-linked substituents selected from the group consisting of NA¹A²;(NA¹A²A³)⁺, NA¹SA², NO₂; and NA¹A²; (e) halogens selected from the groupconsisting of F, Cl, Br, and I; and (f) hydrogen; wherein A¹, A², and A³are selected independently from each other from the group consisting ofhydrogen; substituted or unsubstituted, straight or branched or cyclic,saturated or unsaturated, aliphatic or heteroaliphatic or aromatic orheteroaromatic substituents, wherein said substituents or ring comprisefrom 1 to 6 carbon atoms and from 0 to 5 heteroatoms selected from thegroup consisting of O, S, N, P, and Si; R₂ and R₃ are selectedindependently of each other from the group consisting of a hydrogenatom; a C1-C6 alkyl substituent; a trifluoromethyl substituent; a C1-C6aminoalkyl substituent; a C1-C6 hydroxyalkyl substituent; and C1-C6 analkoxyalkyl substituent; (B) a m-aminophenol compound of the generalformula (II), a physiologically compatible water-soluble salt thereof,or mixtures thereof,

wherein R₄, R₅, R₆, R₇ are substituents selected independently of eachother from the group consisting of: (a) C-linked substituents selectedfrom the group consisting of: (i) substituted or unsubstituted, straightor branched or cyclic, saturated or unsaturated, aliphatic orheteroaliphatic substituents, in particular alkyl or hydroxy substitutedalkyl, and (ii) substituted or unsubstituted, mono- or poly-unsaturatedaromatic or heteroaromatic substituents, in particular aryl orheteroaryl, wherein said C-linked substituents comprise from 1 to 10carbon atoms and from 0 to 5 heteroatoms selected from the groupconsisting of O, F, N, P and Si; (b) S-linked substituents selected fromthe group consisting of SA¹, SO₂A¹, SO₃A¹, SSA¹, SOA¹, SO₂NA¹A², SNA¹A²,and SONA¹A²; (c) O-linked substituents selected from the groupconsisting of OA¹ and ONA¹A²; (d) N-linked substituents selected fromthe group consisting of NA¹A²; (NA¹A²A³)⁺, NA¹SA², NO₂; and NA¹A²; (e)halogens selected from the group consisting of F, Cl, Br, and I; and (f)hydrogen; wherein A¹, A², and A³ are independently selected from eachother from the group consisting of: hydrogen; substituted orunsubstituted, straight or branched or cyclic, saturated or unsaturated,aliphatic or heteroaliphatic or aromatic or heteroaromatic substituents,or A¹ and A² together with nitrogen atoms to which they are bound form aring; wherein said substituents or ring comprise from 1 to 10 carbonatoms and from 0 to 5 heteroatoms selected from the group consisting ofO, S, N, P, and Si; wherein R₈ and R₉ are substituents selectedindependently of each other from the group consisting of: (g) C-linkedsubstituents selected from the group consisting of: (i) substituted orunsubstituted, straight or branched or cyclic, saturated or unsaturated,aliphatic or heteroaliphatic substituents, in particular alkyl orhydroxy substituted alkyl, and (ii) substituted or unsubstituted, mono-or poly-unsaturated aromatic or heteroaromatic substituents, inparticular aryl or heteroaryl, wherein said C-linked substituentscomprise from 1 to 6 carbon atoms and from 0 to 5 heteroatoms selectedfrom the group consisting of O, F, N, P and Si; and (h) hydrogen; and(C) an oxidizing agent.
 2. A composition according to claim 1, whereinthe 1-hexyl/heptyl-4,5-diaminopyrazole compound (I) is a compound withformula (I.1):


3. A composition according to claim 1, wherein the m-aminophenolcompound (II) is selected from the group consisting of:

and combinations thereof.
 4. A composition according to claim 1, furthercomprising a primary intermediate selected from toluene-2,5-diamine,p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine,2-methoxymethyl-p-phenylenediamine,2-(2,5-diamino-4-methoxyphenyl)propane-1,3-diol,2-chloro-p-phenylenediamine, 2-methoxy-p-phenylenediamine,2-((2-(4-amino-phenylamino)-ethyl)-(2-hydroxyethyl)-amino)-ethanol,salts thereof and combination thereof.
 5. A composition according toclaim 1 further comprising at least one additional component selectedfrom the group consisting of alkalizing agents, auxiliary primaryintermediates, auxiliary couplers, direct dyes, thickeners, chelants, pHmodifiers and/or buffering agents, radical scavenger systems andmixtures thereof.
 6. A composition according to claim 1, furthercomprising fatty alcohols comprising from 14 to 30 carbon atoms, oroxyethylenated fatty alcohols comprising from 16 to 30 carbon atoms and2 units or less of ethylene oxide.
 7. A composition according to claim6, further comprising at least one ionic or nonionic surfactant selectedfrom: anionic surfactants selected from C8-C30 alkyl sulfates, anionicsurfactants according to the formula R_(n)X_(m)YM, wherein R isindependently selected from alkyl, alkenyl or alkylaryl groups havingfrom 8 to 30 carbon atoms, X is independently selected from polar groupscomprising at least one carbon atom and at least one oxygen or nitrogenatom, Y is an anionic group selected from carboxylates, sulfates,sulfonates or phosphates, n and m are independently 1 or 2, and M ishydrogen or a salt forming cation and mixture thereof; non-ionicsurfactant comprising one or more polyethyleneoxide chains; cationicsurfactants selected from quaternary ammonium salts or amido-amineshaving at least one fatty chain, preferably comprising at least 16carbon atoms and most preferably at least 20 carbon atoms; or mixturesthereof.
 8. A composition according to claim 7 comprising a mixture ofcetearyl alcohol and dicetyl phosphate and ceteth-10 phosphate.
 9. Acomposition according to claim 1 further comprising a chelant selectedfrom the group consisting of: diethylenetriamine-N,N′,N″-polyacids,diethylenetriaminepentaacetic acid (DTPA),diethylenetriaminepenta(methylene phosphonic acid) (DTPMP),diamine-N,N′-dipolyacid, monoamine monoamide-N,N′-dipolyacid, andN,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid chelants,carboxylic acids, phosphonic acids and polyphosphoric acids, their saltsand derivatives.
 10. A composition according to claim 1 wherein saidoxidizing agent is selected from the group consisting of hydrogenperoxide, sodium periodate, urea peroxide, melamine peroxide,perborates, percarbonates, perphosphates, persilicates, persulfates,oxidizing enzymes such as uricases, oxidases, and peroxidases, a sourceof peroxymonocarbonate ions and mixtures thereof.
 11. A compositionaccording to claim 10 wherein the source of peroxymonocarbonate ionsselected from the group consisting of: sodium, potassium, guanidine,arginine, lithium, calcium, magnesium, barium or ammonium salts ofcarbonate, carbamate and hydrocarbonate ions and mixtures thereof.
 12. Acomposition according to claim 1, wherein said composition is dispensedas a foam.
 13. A method of dyeing hair comprising the steps of: (i)providing a tint component comprising (a) a1-hexyl/heptyl-4,5-diaminopyrazole compound of the general formula (I)as defined in claim 1, a physiologically compatible water-soluble saltthereof or mixtures thereof and; (b) a m-aminophenol compound of thegeneral formula (II) as defined in claim 1, a physiologically compatiblewater-soluble salt thereof or mixtures thereof; (ii) providing adeveloper component comprising (c) an oxidizing agent; (iii) mixing thetint component and the developer component to obtain a composition forthe oxidative dyeing of keratin fibers according to claim 1; and (iv)applying said composition for the oxidative dyeing of keratin fibersonto the hair.
 14. An oxidative hair dyeing kit comprising: (i) a tintcomponent comprising (a) a 1-hexyl/heptyl-4,5-diaminopyrazole compoundof the general formula (I) as defined in claim 1, a physiologicallycompatible water-soluble salt thereof, or mixtures thereof, and (b) am-aminophenol compound of the general formula (II) as defined in claim1, a physiologically compatible water-soluble salt thereof, or mixturesthereof; and ii) a developer component comprising an oxidizing agent.15. A tint component comprising (a) a 1-hexyl/heptyl-4,5-diaminopyrazolecompound of the general formula (I) as defined in claim 1, aphysiologically compatible water-soluble salt thereof, or mixturesthereof, and (b) a m-aminophenol compound of the general formula (II) asdefined in claim 1, a physiologically compatible water-soluble saltthereof or mixtures thereof.